Precise assignment with H-1, C-13 and some two dimensional NMR measurements showed that sulfonation reaction by concentrated sulfuric acid at 30 degrees C of fluorine-containing poly(arylene ether ketone) copolymers derived from 4,4'-bis(2,4,5,6-pentafluorobenzoyl)diphenyl ether (BPDE) and 9,9-bis(4-hydroxypehnyl)fluorene (HF) and 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (6FBA) yielded quantitative introduction of sulfonic groups onto 2- and 7-positions of fluorene ring in HF unit. A series of sulfonated poly(arylene ether ketone)s with different ion exchange capacity was prepared by using this method with different compositions of HF and 6FBA, and membranes obtained from these polymers were characterized by TGA, moisture and water uptake, proton conductivity, methanol permeability, and Fenton testing. These membranes showed sufficient thermal stability, high proton conductivity at high humidified condition for PEFC and good balance in proton conductivity in water and methanol permeability for DMFC. On the other hand, they showed relatively high swelling by water probably due to weak intermolecular interaction caused by the existence of fluorine atoms in the polymer structure. (C) 2012 Elsevier Ltd. All rights reserved.